Stable Hexagonal V 2 B 2 Monolayer as a Promising Nonprecious Electrocatalyst for Hydrogen Evolution Reaction: Insights from First‐Principles Calculations

The development of efficient, cost‐effective, and durable electrocatalysts for the hydrogen evolution reaction (HER) is critical for advancing sustainable energy systems and enabling the widespread adoption of hydrogen‐based energy technologies. In this study, we discover a stable hexagonal V 2 B 2 monolayer that serves as a promising HER catalyst via an unbiased swarm‐intelligence structural method as implemented in CALYPSO code. First‐principles calculations show that the predicted V 2 B 2 monolayer exhibits excellent metallic properties and promising catalytic activity for HER, suggesting CALYPSO's utility for accelerating the discovery of efficient electrocatalysts. Further doping engineering, incorporating transition metals (TM′ = Sc, Y, Ti, Zr, Hf), reveals that the introduction of Sc, Y, and Zr significantly enhances the catalytic performance. Bader charge analysis reveals a linear correlation between the electron gain by the hydrogen atom and Δ G H* , suggesting that this relationship could serve as an effective descriptor for HER activity in TM'‐doped V 2 B 2 systems. Our findings provide valuable insights into nonprecious HER electrocatalysts and contribute to a deeper understanding of high catalytic performance in newly proposed 2D HER catalysts.